Colorants

ABSTRACT

A composition for coloring keratin fibers, containing an indoline, an indole, or a derivative thereof in combination with at least one amino acid or oligopeptide. The composition is useful for coloring human hair and restoring grey hair to its natural color. The formulation can be applied with atmospheric oxygen as the sole oxidizing agent.

[0001] This application claims benefit of U.S. Provisional ApplicationSerial No. 60/093,926 filed Jul. 23, 1998.

BACKGROUND OF THE INVENTION

[0002] This invention relates to formulations for coloring keratinfibers, more particularly human hair, which contain special dyeprecursors of the indole or indoline type and a component forintensifying and/or shading the color, to the use of this component forintensifying and/or shading colors and to corresponding coloringprocesses.

[0003] Among the various products available for the cosmetic treatmentof the human body, formulations for modifying or shading the color ofthe hair occupy a prominent position. Disregarding blonding preparationswhich lighten the hair oxidatively by degrading the natural hair dyes,two types of colorants have long been of importance in the coloring ofhair:

[0004] So-called oxidation colorants are used for permanent, intensivecolors with corresponding fastness properties. Oxidation colorantsnormally contain oxidation dye precursors, so-called primaryintermediates and secondary intermediates. The primary intermediatesform the actual dyes with one another or by coupling with one or moresecondary intermediates under the influence of oxidizing agents oratmospheric oxygen. Although oxidation colorants are distinguished byexcellent coloring results, they can also be attended by disadvantagesfor certain narrow circles of people. Thus, certain dye precursors cancause unwanted skin irritation in so-called Apara-allergics≅. Inaddition, oxidation dyes are generally developed with oxidizing agents,more particularly hydrogen peroxide. In the event of frequentapplication by people with sensitive hair, this can cause harm or evendamage to the hair structure which has to be repaired with specialhair-care products. It is also important not to underestimate the numberof people who, in the context of the popular Anatural-versus-chemical≅debate, avoid using chemical products wherever possible because of theirpersonal feelings.

[0005] Colorants or tints containing substantive dyes as their coloringcomponent are normally used for temporary colors. Substantive dyes arebased on dye molecules which are directly absorbed onto the hair and donot require an oxidative process for developing the color. Dyes such asthese include, for example, henna which has been used since ancienttimes for coloring the body and hair.

[0006] However, since in the eyes of many consumers both coloringprocesses are tainted by a hint of the Aartificial≅ with its negativeassociations, a new coloring process has recently attracted considerableattention. In this process, precursors of the natural hair dye melaninare applied to the hair and, through oxidative processes in the hair,form near-natural dyes. A corresponding process using5,6-dihydroxyindoline as dye precursor is described in EP-B1 530 229. Byapplication and, more particularly, frequent application of formulationscontaining 5,6-dihydroxyindoline, grey hair can be restored to itsnatural color. The color can be developed with atmospheric oxygen assole oxidizing agent so that there is no need to use other oxidizingagents.

[0007] Under the described conditions, however, satisfactory results canonly be achieved in people who, before Agoing grey≅, had medium blond todark brown hair. Accordingly, there has been no shortage of attempts tomodify this known coloring process in such a way that even originallyred and, above all, dark to black hair can be restored to its originalcolor.

[0008] One method of obtaining dark to black color tones, particularlythose described by experts as Aflat≅, is the subject of German patentapplication 197 32 975.6 to which reference is expressly made,particularly in regard to the prior art literature cited therein. Thesolution proposed in this patent application is to add conventionalsecondary intermediates. Although the color can be developed withatmospheric oxygen alone, the use of at least one other oxidizing agentis recommended as a preferred alternative.

[0009] However, in view of the above-mentioned reservations of manyconsumers, there is still a need for a formulation which restores greyhair to its natural color, even in people with originally dark to blackhair, without any need for purely synthetic dye components or to useother oxidizing agents than atmospheric oxygen.

[0010] It has now surprisingly been found that the problem stated abovecan be solved by application of a formulation which, besides known dyeprecursors of the indole or indoline type, contains at least one aminoacid or oligopeptide.

DESCRIPTION OF THE INVENTION

[0011] Accordingly, the present invention relates to formulations forcoloring keratin fibers, more particularly human hair, containing a dyeprecursor selected from the group consisting of indoline derivatives andindole derivatives, characterized in that it additionally contains atleast one amino acid or oligopeptide.

[0012] Amino acids in the context of the invention are substances whichcontain at least one amino group and at least one —COOH or —SO₃H group.

[0013] Preferred amino acids are aminocarboxylic acids, moreparticularly α-aminocarboxylic acids and ω-aminocarboxylic acids. Amongthe α-aminocarboxylic acids, arginine, lysine, ornithine and histidineare particularly preferred.

[0014] The amino acids are preferably added to the formulationsaccording to the invention in free form. However, the amino acids mayalso be used in salt form. Preferred salts are the compounds containinghydrohalic acids, more particularly hydrochlorides and hydrobromides.

[0015] A particularly preferred amino acid is arginine used inparticular in free form but also as the hydrochloride.

[0016] The present invention does of course also encompass formulationscontaining two or more amino acids or oligopeptides. In this case,combinations of arginine with another amino acid or oligopeptide arepreferred.

[0017] In addition, the amino acids may also be used in the form ofoligopeptides and protein hydrolyzates providing steps are taken toensure that the necessary quantities of compounds conforming to thedefinition of amino acids according to the invention are present.Reference is expressly made in this connection to the disclosure ofDE-OS 22 15 303.

[0018] The formulations according to the invention contain the aminoacid or oligopeptide in quantities of preferably 0.1 to 10% by weightand more preferably 1 to 4% by weight, based on the formulation as awhole.

[0019] Hair colorants, more particularly those where the color isdeveloped oxidatively with atmospheric oxygen or other oxidizing agents,such as hydrogen peroxide, are normally adjusted to a mildly acidic oralkaline pH value, i.e. to a pH value in the range from about 5 to 11.To this end, the colorants contain alkalizing agents, normally alkalimetal or alkaline earth metal hydroxides, ammonia or organic amines.

[0020] In one special embodiment of the present invention, the aminoacid or the oligopeptide is used not only to promote color development,but also at least partly as an alkalizing agent. Accordingly, aminoacids and oligopeptides of which 2.5% by weight solutions in water havea pH value of 9 or higher are preferably used in this embodiment. Onesuch amino acid is the preferred arginine. In this particularembodiment, the other alkalizing agent is selected from the groupconsisting of monoethanolamine, monoisopropanolamine,2-amino-2-methylpropanol, 2-amino-2-methyl-1,3-propanediol,2-amino-2-ethyl-1,3-propanediol, 2-amino-2-methylbutanol andtriethanolamine and alkali metal and alkaline earth metal hydroxides.Within this group, monoethanolamine, triethanolamine and2-amino-2-methylpropanol and 2-amino-2-methyl-1,3-propanediol areparticularly preferred. ω-Amino acids, such as ω-aminocaproic acid, arealso preferably used as alkalizing agents in this embodiment of theinvention.

[0021] Particularly advantageous properties are exhibited byformulations in which the amino acid or the oligopeptide and the otheralkalizing agent are present in a ratio by weight of 1:5 to 5:1.Quantity ratios of 1:2 to 2:1 have proved to be particularly suitable.

[0022] The formulations according to the invention contain a dyeprecursor of the indole or indoline type as another compulsorycomponent.

[0023] According to the invention, preferred indoles and indolines arethose which contain at least one hydroxy or amino group, preferably as asubstituent on the six-membered ring. These groups may carry othersubstituents, for example in the form of etherification oresterification of the hydroxy group or alkylation of the amino group.Compounds containing two of these groups, particularly two hydroxygroups, of which one or both may be etherified or esterified areparticularly preferred.

[0024] According to the invention, particularly preferred dye precursorsare derivatives of indoline, such as 5,6-dihydroxyindoline,N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline,N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline,5,6-dihydroxyindoline-2-carboxylic acid, 4-, 6- and 7-hydroxyindoline,6-aminoindoline and 4-aminoindoline.

[0025] Most particularly preferred dye precursors are derivatives of5,6-dihydroxyindoline corresponding to formula (Ia):

(Ia)

[0026] in which—independently of one another—

[0027] R¹ is hydrogen, a C₁₋₄ alkyl group or a C₁₋₄ hydroxyalkyl group,

[0028] R² is hydrogen or a —COOH group which may even be present as asalt with a physiologically compatible anion,

[0029] R³ is hydrogen or a C₁₋₄ alkyl group,

[0030] R⁴ is hydrogen, a C₁₋₄ alkyl group or a group —CO—R⁶ where R⁶ isa C₁₋₄ alkyl group,

[0031] R⁵ stands for one of the groups mentioned for R⁴,

[0032] or a physiologically compatible salt of these compounds with anorganic or inorganic acid.

[0033] According to the invention, preferred representatives are5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline,N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline,N-butyl-5,6-dihydroxyindoline. The parent compound,5,6-dihydroxyindoline, is most particularly preferred.

[0034] According to the invention, preferred indoles are5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole,N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole,N-butyl-5,6-dihydroxyindole, 5,6-dihydroxyindole-2-carboxylic acid, 4-,6- and 7-hydroxyindole, 6-aminoindole and 4-aminoindole.

[0035] Particular preference is attributed to derivatives of5,6-dihydroxyindole corresponding to formula (Ib):

(Ib)

[0036] in which—independently of one another—

[0037] R¹ is hydrogen, a C₁₋₄ alkyl group or a C₁₋₄ hydroxyalkyl group,

[0038] R² is hydrogen or a —COOH group which may even be present as asalt with a physiologically compatible anion,

[0039] R³ is hydrogen or a C₁₋₄ alkyl group,

[0040] R⁴ is hydrogen, a C₁₋₄ alkyl group or a group —CO—R⁶ where R⁶ isa C₁₋₄ alkyl group,

[0041] R⁵ stands for one of the groups mentioned for R⁴,

[0042] or a physiologically compatible salt of these compounds with anorganic or inorganic acid.

[0043] According to the invention, preferred representatives are5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole,N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole,N-butyl-5,6-dihydroxyindole. The parent compound, 5,6-dihydroxyindole,is most particularly preferred.

[0044] The indoline and indole derivatives present in the formulationsaccording to the invention may be used both as free bases and in theform of their physiologically compatible salts with inorganic or organicacids, for example hydrochlorides, sulfates and hydrobromides.

[0045] The indole or indoline derivatives are present in theformulations according to the invention in quantities of normally 0.05to 10% by weight and preferably 0.2 to 5% by weight.

[0046] The present invention does of course also encompass formulationswhich contain more than one indoline or indole derivative or mixtures ofindoline or indole derivatives.

[0047] In one particularly preferred embodiment, the formulationsaccording to the invention contain no dyes or dye precursors other thanthe indoles or indolines mentioned.

[0048] In principle, however, other dye components or dye precursorscould be used.

[0049] In the embodiments containing such additional compounds, thefollowing substances are preferred:

[0050] Preferred primary intermediates:

[0051] p-phenylenediamine, p-toluylenediamine, p-aminophenol,o-aminophenol, 1-(2′-hydroxyethyl)-2,5-diaminobenzene,N,N-bis-(2-hydroxyethyl)-p-phenylenediamine,2-(2,5-diaminophenoxy)-ethanol,1-phenyl-3-carboxyamido-4-amino-5-pyrazolone, 4-amino-3-methylphenol,2,4,5,6-tetraaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine,4-hydroxy-2,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine,2-dimethylamino-4,5,6-triaminopyrimidine,2-hydroxyethylaminomethyl-4-aminophenol, 4,4′-diaminodiphenylamine,4-amino-3-fluorophenol, 2-aminomethyl-4-aminophenol,2-hydroxymethyl-4-aminophenol, bis-(2-hydroxy-5-aminophenyl)-methane,1,4-bis-(4-aminophenyl)-diazacycloheptane,1,3-bis-(N-(2-hydroxyethyl)-N-(4-aminophenylamino))-2-propanol,4-amino-2-(2-hydroxyethoxy)-phenol and 4,5-diaminopyrazole derivativesaccording to EP 0 740 741 and WO 94/08970 such as, for example,4,5-diamino-1-(2′-hydroxyethyl)-pyrazole.

[0052] Particularly preferred primary intermediates:

[0053] p-phenylenediamine, p-toluylenediamine, p-aminophenol,1-(2′-hydroxyethyl)-2,5-diaminobenzene, 4-amino-3-methylphenol,4-amino-2-((diethylamino)-methyl)-phenol, 2,4,5,6-tetraaminopyrimidine,2-hydroxy-4,5,6-triaminopyrimidine and4-hydroxy-2,5,6-triaminopyrimidine.

[0054] Preferred secondary intermediates:

[0055] m-aminophenol and derivatives thereof such as, for example,5-amino-2-methylphenol, 5-(3-hydroxypropylamino)-2-methylphenol,3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxy-ethanol,3-amino-6-methoxy-2-methylaminophenol, 2,6-dimethyl-3-aminophenol,3-trifluoroacetylamino-2-chloro-6-methylphenol,5-amino-4-chloro-2-methylphenol, 5-amino-4-methoxy-2-methylphenol,5-(2′-hydroxyethyl)-amino-2-methylphenol, 3-(diethylamino)-phenol,N-cyclopentyl-3-aminophenol, 1,3-dihydroxy-5-(methyl-amino)-benzene,3-(ethylamino)-4-methylphenol and 2,4-dichloro-3-aminophenol,

[0056] o-aminophenol and derivatives thereof,

[0057] m-diaminobenzene and derivatives thereof such as, for example,2,4-diaminophenoxyethanol, 1,3-bis-(2,4-diaminophenoxy)-propane,1-methoxy-2-amino-4-(2′-hydroxyethylamino)-benzene,1,3-bis-(2,4-diaminophenyl)-propane,2,6-bis-(2-hydroxyethylamino)-1-methylbenzene and1-amino-3-bis-(2′-hydroxyethyl)-aminobenzene,

[0058] o-diaminobenzene and derivatives thereof such as, for example,3,4-diaminobenzoic acid and 2,3-diamino-1-methylbenzene,

[0059] di- and trihydroxybenzene derivatives such as, for example,resorcinol, resorcinol monomethyl ether, 2-methyl resorcinol, 5-methylresorcinol, 2,5-dimethyl resorcinol, 2-chlororesorcinol,4-chlororesorcinol, pyrogallol and 1,2,4-trihydroxybenzene,

[0060] pyridine derivatives such as, for example, 2,6-dihydroxypyridine,2-amino-3-hydroxypyridine, 2-amino-5-chloro-3-hydroxypyridine,3-amino-2-methylamino-6-methoxypyridine,2,6-dihydroxy-3,4-dimethylpyridine, 2,6-dihydroxy-3,4-diaminopyridine,2,6-dihydroxy-4-methylpyridine, 2,6-diaminopyridine,2,3-diamino-6-methoxypyridine and 3,5-diamino-2,6-dimethoxypyridine,

[0061] naphthalene derivatives such as, for example, 1-naphthol,2-methyl-1-naphthol, 2-hydroxymethyl-1-naphthol,2-hydroxyethyl-1-naphthol, 1,5-dihydroxynaphthalene,1,6-dihdroxynaphthalene, 1,7-dihdroxynaphthalene,1,8-dihdroxynaphthalene, 2,7-dihdroxynaphthalene and2,3-dihdroxynaphthalene,

[0062] morpholine derivatives such as, for example,6-hydroxybenzomorpholine and 6-aminobenzomorpholine,

[0063] quinoxaline derivatives such as, for example,6-methyl-1,2,3,4-tetrahydroquinoxaline,

[0064] pyrazole derivatives such as, for example,1-phenyl-3-methylpyrazol-5-one,

[0065] indole derivatives such as, for example, 4-hydroxyindole,6-hydroxyindole and 7-hydroxyindole,

[0066] methylenedioxybenzene derivatives such as, for example,3,4-methylenedioxyphenol, 1-hydroxy-3,4-methylenedioxybenzene,1-amino-3,4-methylenedioxybenzene and1-(2′-hydroxyethyl)-amino-3,4-methylenedioxybenzene.

[0067] Particularly preferred secondary intermediates:

[0068] 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene,3-aminophenol, 5-amino-2-methylphenol, 2-amino-3-hydroxypyridine,resorcinol, 4-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol,2-methyl resorcinol, 5-methyl resorcinol, 2,5-dimethyl resorcinol,2,6-dihydroxy-3,4-diaminopyridine.

[0069] Preferred substantive dyes are the compounds known under theInternational names or commercial names of HC Yellow 2, HC Yellow 4, HCYellow 5, HC Yellow 6, Basic Yellow 57, Disperse Orange 3, HC Red 3, HCRed BN, Basic Red 76, HC Blue 2, HC Blue 12, Disperse Blue 3, Basic Blue99, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9,Basic Brown 16 and Basic Brown 17 and also4-amino-2-nitrodiphenylamine-2′-carboxylic acid,6-nitro-1,2,3,4-tetrahydroquinoxaline, hydroxyethyl-2-nitrotoluidine,picramic acid, 2-amino-6-chloro-4-nitrophenol,4-ethylamino-3-nitrobenzoic acid and2-chloro-6-ethylamino-1-hydroxy-4-nitrobenzene. Other preferredsubstantive dyes are naturally occurring dyes such as, for example,henna red, henna neutral, henna black, camomile blossom, sandalwood,black tea, black alder bark, sage, logwood, madder root, catechu, sedreand alkanet.

[0070] The oxidation dye precursors or the substantive dyes do not haveto be single compounds. Instead, the hair colorants according to theinvention—due to the processes used for producing the individualdyes—may contain small quantities of other components providing they donot adversely affect the coloring result or have to be ruled out forother reasons, for example toxicological reasons.

[0071] With regard to the dyes suitable for use in the hair coloring andtinting formulations according to the invention, reference is alsospecifically made to Ch. Zviak=s work The Science of Hair Care, Chapter7 (pages 248-250; Substantive Dyes) and Chapter 8, pages 264-267;Oxidation Dye Precursors), published as Vol. 7 of the SeriesADermatology≅ (Editors: Ch. Culnan and H. Maibach), Marcel Dekker Inc.,New York/Basel, 1986 and to the AEuropäische Inventar derKosmetik-Rohstoffe≅ published by the Europäische Gemeinschaft andavailable in diskette form from the Bundesverband Deutscher Industrie-und Handelsunternehmen für Arzneimittel, Reformwaren undKorperpflegemittel e.V., Mannheim, Germany.

[0072] Both the oxidation dye precursors and the substantive dyes arepresent in the formulations according to the invention in quantities ofpreferably 0.01 to 20% by weight and preferably 0.5 to 5% by weight,based on the formulation as a whole.

[0073] Preferred formulations containing other dyes or dye precursorsare those which do not contain an oxidation dye precursor of the primaryintermediate type. In this embodiment of the invention, thecorresponding formulations contain an oxidation dye precursor of thesecondary intermediate type and, if desired, substantive dyes.

[0074] Other preferred formulations are those which do not contain anoxidation dye precursor of the secondary intermediate type. Theseformulations are also preferably free from oxidation dye precursors ofthe primary intermediate type, but may contain a substantive dye,preferably from the series of naturally occurring dyes.

[0075] To produce the colorants according to the invention, thecompulsory and optional constituents mentioned above are incorporated ina suitable water-containing carrier. For coloring hair, such carriersare, for example, cremes, emulsions, gels or even surfactant-containingfoaming solutions, for example shampoos, foam aerosols or otherformulations suitable for application to the hair.

[0076] The hair colorants according to the invention are adjusted to apH value of preferably 5 to 11 and, more preferably, 7 to 10.

[0077] The colorants according to the invention may also contain any ofthe known active substances, additives and auxiliaries typical of suchformulations. In many cases, the colorants contain at least onesurfactant, both anionic and zwitterionic, ampholytic, nonionic andcationic surfactants being suitable in principle. In many cases,however, it has been found to be of advantage to select the surfactantsfrom anionic, zwitterionic or nonionic surfactants. Anionic surfactantscan be particularly useful.

[0078] Suitable anionic surfactants for the hair colorants according tothe invention are any anionic surface-active substances suitable for useon the human body. Such substances are characterized by awater-solubilizing anionic group such as, for example, a carboxylate,sulfate, sulfonate or phosphate group and a lipophilic alkyl groupcontaining around 10 to 22 carbon atoms. In addition, glycol orpolyglycol ether groups, ether, amide and hydroxyl groupsand—generally—ester groups may also be present in the molecule. Thefollowing are examples of suitable anionic surfactants—in the form ofthe sodium, potassium and ammonium salts and the mono-, di- andtrialkanolammonium salts containing 2 or 3 carbon atoms in the alkanolgroup:

[0079] linear and branched fatty acids containing 8 to 22 carbon atoms(soaps),

[0080] ether carboxylic acids corresponding to the formulaR—O—(CH₂—CH₂O)_(x)—CH₂—COOH, in which R is a linear alkyl groupcontaining 10 to 22 carbon atoms and x=0 or 1 to 16,

[0081] acyl sarcosides containing 10 to 18 carbon atoms in the acylgroup,

[0082] acyl taurides containing 10 to 18 carbon atoms in the acyl group,

[0083] acyl isethionates containing 10 to 18 carbon atoms in the acylgroup,

[0084] sulfosuccinic acid mono- and dialkyl esters containing 8 to 18carbon atoms in the alkyl group and sulfosuccinic acid monoalkylpolyoxyethyl esters containing 8 to 18 carbon atoms in the alkyl groupand 1 to 6 oxyethyl groups,

[0085] linear alkane sulfonates containing 12 to 18 carbon atoms,

[0086] linear α-olefin sulfonates containing 12 to 18 carbon atoms,

[0087] α-sulfofatty acid methyl esters of fatty acids containing 12 to18 carbon atoms,

[0088] alkyl sulfates and alkyl polyglycol ether sulfates correspondingto the formula R—O(CH₂—CH₂O)_(x)—SO₃H, in which R is a preferably linearalkyl group containing 10 to 18 carbon atoms and x=0 or 1 to 12,

[0089] mixtures of surface-active hydroxysulfonates according to DE-A-3725 030,

[0090] sulfated hydroxyalkyl polyethylene and/or hydroxyalkylenepropylene glycol ethers according to DE-A-37 23 354,

[0091] sulfonates of unsaturated fatty acids containing 12 to 24 carbonatoms and 1 to 6 double bonds according to DE-A-39 26 344,

[0092] esters of tartaric acid and citric acid with alcohols in the formof addition products of around 2 to 15 molecules of ethylene oxideand/or propylene oxide with fatty alcohols containing 8 to 22 carbonatoms.

[0093] Preferred anionic surfactants are alkyl sulfates, alkylpolyglycol ether sulfates and ether carboxylic acids containing 10 to 18carbon atoms in the alkyl group and up to 12 glycol ether groups in themolecule and, in particular, salts of saturated and, more particularly,unsaturated C₈₋₂₂ carboxylic acids, such as oleic acid, stearic acid,isostearic acid and palmitic acid.

[0094] In the context of the invention, zwitterionic surfactants aresurface-active compounds which contain at least one quaternary ammoniumgroup and at least one —COO⁽⁻⁾ or —SO₃ ⁽⁻⁾ group in the molecule.Particularly suitable zwitterionic surfactants are the so-calledbetaines, such as N-alkyl-N,N-dimethyl ammonium glycinates, for examplecocoalkyl dimethyl ammonium glycinate, N-acylaminopropyl-N,N-dimethylammonium glycinates, for example cocoacylaminopropyl dimethyl ammoniumglycinate, and 2-alkyl-3-carboxymethyl-3-hydroxyethyl imidazolinescontaining 8 to 18 carbon atoms in the alkyl or acyl group andcocoacylaminoethyl hydroxyethyl carboxymethyl glycinate. A preferredzwitterionic surfactant is the fatty acid amide derivative known by theCTFA name of Cocamidopropyl Betaine.

[0095] Ampholytic surfactants are surface-active compounds which, inaddition to a C₈₋₁₈ alkyl or acyl group, contain at least one free aminogroup and at least one —COOH or —SO₃H group in the molecule and whichare capable of forming inner salts. Examples of suitable ampholyticsurfactants are N-alkyl glycines, N-alkyl propionic acids, N-alkylaminobutyric acids, N-alkyl iminodipropionic acids,N-hydroxyethyl-N-alkyl amidopropyl glycines, N-alkyl taurines, N-alkylsarcosines, 2-alkyl aminopropionic acids and alkyl aminoacetic acidscontaining around 8 to 18 carbon atoms in the alkyl group. Particularlypreferred ampholytic surfactants are N-cocoalkyl aminopropionate,cocoacyl aminoethyl aminopropionate and C₁₂₋₁₈ acyl sarcosine.

[0096] Nonionic surfactants contain, for example, a polyol group, apolyalkylene glycol ether group or a combination of polyol andpolyglycol ether groups as the hydrophilic group. Examples of suchcompounds are

[0097] products of the addition of 2 to 30 moles of ethylene oxideand/or 0 to 5 moles of propylene oxide to linear fatty alcoholscontaining 8 to 22 carbon atoms, to fatty acids containing 12 to 22carbon atoms and to alkylphenols containing 8 to 15 carbon atoms in thealkyl group,

[0098] C₁₂₋₂₂ fatty acid monoesters and diesters of products of theaddition of 1 to 30 moles of ethylene oxide to glycerol,

[0099] C₈₋₂₂ alkyl mono- and oligoglycosides and ethoxylated analogsthereof,

[0100] products of the addition of 5 to 60 moles of ethylene oxide tocastor oil and hydrogenated castor oil,

[0101] products of the addition of ethylene oxide to sorbitan fatty acidesters,

[0102] products of the addition of ethylene oxide to fatty acidalkanolamides.

[0103] Examples of cationic surfactants suitable for use in the hairtreatment formulations according to the invention are, in particular,quaternary ammonium compounds. Preferred quaternary ammonium compoundsare ammonium halides, such as alkyl trimethyl ammonium chlorides,dialkyl dimethyl ammonium chlorides and trialkyl methyl ammoniumchlorides, for example cetyl trimethyl ammonium chloride, stearyltrimethyl ammonium chloride, distearyl dimethyl ammonium chloride,lauryl dimethyl ammonium chloride, lauryl dimethyl benzyl ammoniumchloride and tricetyl methyl ammonium chloride. Other cationicsurfactants suitable for use in accordance with the invention are thequaternized protein hydrolyzates.

[0104] Also suitable for use in accordance with the invention arecationic silicone oils such as, for example, the commercially availableproducts 02-7224 (manufacturer: Dow Corning; a stabilized trimethylsilyl amodimethicone), Dow Corning 929 Emulsion (containing ahydroxylamino-modified silicone which is also known as Amodimethicone),SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer:Wacker) and Abil7-Quat 3270 and 3272 (manufacturer: Th. Goldschmidt;diquaternary polydimethyl siloxanes, Quaternium-80).

[0105] Alkyl amidoamines, particularly fatty acid amidoamines, such asthe stearyl amidopropyl dimethyl amine obtainable as Tego Amid7S 18, aredistinguished not only by their favorable conditioning effect, but alsoand in particular by their ready biodegradability.

[0106] Quaternary ester compounds, so-called Aesterquats≅, such as themethyl hydroxyalkyl dialkoyloxyalkyl ammonium methosulfates marketedunder the trade name of Stepantex7 and the corresponding productscommercially available as Dehyquart7, are also readily biodegradable.

[0107] One example of a quaternary sugar derivative suitable for use asa cationic surfactant is the commercially available product Glucquat7100(CTFA name: Lauryl Methyl Gluceth-10 Hydroxypropyl Dimonium Chloride).

[0108] The compounds containing alkyl groups used as surfactants may besingle compounds. In general, however, these compounds are produced fromnative vegetable or animal raw materials so that mixtures with differentalkyl chain lengths dependent upon the particular raw material areobtained.

[0109] The surfactants representing addition products of ethylene and/orpropylene oxide with fatty alcohols or derivatives of these additionproducts may be both products with a Anormal≅ homolog distribution andproducts with a narrow homolog distribution. Products with a Anormal≅homolog distribution are mixtures of homologs which are obtained in thereaction of fatty alcohol and alkylene oxide using alkali metals, alkalimetal hydroxides or alkali metal alcoholates as catalysts. By contrast,narrow homolog distributions are obtained when, for example,hydrotalcites, alkaline earth metal salts of ether carboxylic acids,alkaline earth metal oxides, hydroxides or alcoholates are used ascatalysts. The use of products with a narrow homolog distribution can beof advantage.

[0110] Other active substances, auxiliaries and additives are, forexample,

[0111] nonionic polymers such as, for example, vinyl pyrrolidone/vinylacrylate copolymers, polyvinyl pyrrolidone and vinyl pyrrolidone/vinylacetate copolymers and polysiloxanes,

[0112] cationic polymers, such as quaternized cellulose ethers,polysiloxanes containing quaternary groups, dimethyl diallyl ammoniumchloride polymers, acrylamide/dimethyl diallyl ammonium chloridecopolymers, dimethyl aminoethyl methacrylate/vinyl pyrrolidonecopolymers quaternized with diethyl sulfate, vinylpyrrolidone/imidazolinium methochloride copolymers and quaternizedpolyvinyl alcohol,

[0113] zwitterionic and amphoteric polymers such as, for example,acrylamidopropyl/trimethyl ammonium chloride/acrylate copolymers andoctyl acrylamide/methyl methacrylate/tert.butyl aminoethylmethacrylate/2-hydroxypropyl methacrylate copolymers,

[0114] anionic polymers such as, for example, polyacrylic acids,crosslinked polyacrylic acids, vinyl acetate/crotonic acid copolymers,vinyl pyrrolidone/vinyl acrylate copolymers, vinyl acetate/butylmaleate/isobornyl acrylate copolymers, methyl vinyl ether/maleicanhydride copolymers and acrylic acid/ethyl acrylate/N-tert.butylacrylamide terpolymers,

[0115] thickeners, such as agar agar, guar gum, alginates, xanthan gum,gum arabic, karaya gum, carob bean flour, linseed gums, dextrans,cellulose derivatives, for example methyl cellulose, hydroxyalkylcellulose and carboxymethyl cellulose, starch fractions and derivatives,such as amylose, amylopectin and dextrins, clays such as, for example,bentonite or fully synthetic hydrocolloids such as, for example,polyvinyl alcohol,

[0116] structurants, such as glucose, maleic acid and lactic acid,

[0117] hair-conditioning compounds, such as phospholipids, for examplesoya lecithin, egg lecithin and kephalins, and also silicone oils,

[0118] protein hydrolyzates, more particularly elastin, collagen,keratin, milk protein, soya protein and wheat protein hydrolyzates,condensation products thereof with fatty acids and quaternized proteinhydrolyzates,

[0119] perfume oils, dimethyl isosorbide and cyclodextrins,

[0120] solvents and solubilizers, such as ethanol, isopropanol, ethyleneglycol, propylene glycol, glycerol and diethylene glycol,

[0121] antidandruff agents, such as Piroctone Olamine and Zinc Omadine,

[0122] other substances for adjusting the pH value, for example α- andβ-hydroxycarboxylic acids,

[0123] active substances, such as panthenol, pantothenic acid,allantoin, pyrrolidone carboxylic acids and salts thereof, plantextracts and vitamins,

[0124] cholesterol,

[0125] UV filters,

[0126] consistency promoters, such as sugar esters, polyol esters orpolyol alkyl ethers,

[0127] fats and waxes, such as spermaceti, beeswax, montan wax,paraffins, fatty alcohols and fatty acid esters,

[0128] fatty acid alkanolamides,

[0129] complexing agents, such as EDTA, NTA and phosphonic acids,

[0130] swelling and penetration agents, such as glycerol, propyleneglycol monoethyl ether, carbonates, hydrogen carbonates, guanidines,ureas and primary, secondary and tertiary phosphates,

[0131] opacifiers, such as latex,

[0132] pearlescers, such as ethylene glycol mono- and distearate,

[0133] propellents, such as propane/butane mixtures, N₂O, dimethylether, CO₂ and air and

[0134] antioxidants.

[0135] To produce the colorants according to the invention, theconstituents of the water-containing carrier are used in the usualquantities for this purpose. For example, emulsifiers are used inconcentrations of 0.5 to 30% by weight while thickeners are used inconcentrations of 0.1 to 25% by weight, based on the colorant as awhole.

[0136] In one preferred embodiment, the color is developed withatmospheric oxygen as sole oxidizing agent.

[0137] In principle, however, a chemical oxidizing agent may also beused, particularly in cases where the formulations additionally containoxidation dye precursors of the primary intermediate and secondaryintermediate type. The same applies when human hair is to be not onlycolored, but also lightened. Particularly suitable oxidizing agents arehydrogen peroxide or addition products thereof with urea, melamine orsodium borate. Oxidation may also be carried out with enzymes. In thiscase, the enzymes may be used both to produce oxidizing per compoundsand to enhance the effect of an oxidizing agent present in smallquantities. One example of an enzymatic process is the procedure wherebythe effect of small quantities (for example 1% and less, based on theformulation as a whole) of hydrogen peroxide is enhanced by peroxidases.

[0138] The preparation of the oxidizing agent is preferably mixed withthe preparation of the oxidation dye precursors immediately beforecoloring of the hair. The ready-to-use hair coloring preparation formedshould have a pH value in the range from 6 to 10. In a particularlypreferred embodiment, the hair colorant is used in a mildly alkalinemedium. The application temperatures may be in the range from 15 to 40°C. but are preferably at the temperature of the scalp. After a contacttime of about 5 to 45 and preferably 15 to 30 minutes, the hair colorantis removed from the hair to be colored by rinsing. There is no need forthe hair to be washed with a shampoo where a carrier of high surfactantcontent, for example a coloring shampoo, has been used.

[0139] In the particular case of hair which is difficult to color, thepreparation containing the oxidation dye precursors may be applied tothe hair without preliminary mixing with the oxidation component. Theoxidation component is applied after a contact time of 20 to 30 minutes,optionally after rinsing. After another contact time of 10 to 20minutes, the hair is rinsed and, if desired, shampooed. In a firstvariant of this embodiment where the preliminary application of the dyeprecursors is intended to improve penetration into the hair, thecorresponding formulation is adjusted to a pH value of about 4 to 7. Ina second variant, oxidation with air is initially carried out, theformulation applied preferably having a pH value of 7 to 10. In thesubsequent accelerated post-oxidation phase, it can be of advantage touse acidified peroxydisulfate solutions as the oxidizing agent.

[0140] Whichever of the processes mentioned above is used to apply thecolorant according to the invention, development of the color may besupported and enhanced by adding certain metal ions to the colorant.Examples of such metal ions are Zn²⁺, Cu²⁺, Fe²⁺, Fe³⁺, Mn²⁺, Mn⁴⁺, Li⁺,Mg²⁺, Ca²⁺ and Al³⁺. Zn²⁺, Cu²⁺ and Mn²⁺ are particularly suitable.Basically, the metal ions may be used in the form of a physiologicallycompatible salt. Preferred salts are the acetates, sulfates, halides,lactates and tartrates. Zinc sulfate is a particularly preferred metalsalt. Development of the hair color can be accelerated and the colortone can be influenced as required through the use of these metal salts.

[0141] The present invention also relates to the use of an amino acid oroligopeptide for intensifying and/or shading the colors in the coloringof keratin fibers with formulations containing an indoline derivative oran indole derivative as dye precursors.

[0142] The present invention also relates to a process for coloringhuman hair in which one of the formulations mentioned above is appliedto the hair and the color is subsequently developed. In a preferredembodiment, the color is developed with atmospheric oxygen.

[0143] In one particular embodiment of this process, the final color isdeveloped by repeated application of the formulation, followed aftereach application by oxidation with air. The formulation is preferablyapplied at intervals of about 1 day to about 2 weeks. Special tones canbe selectively obtained in this way.

[0144] The following Examples are intended to illustrate the invention.

EXAMPLES

[0145] 1. Coloring

[0146] Colorants with the compositions shown in Table 1 were firstprepared [all quantities in grams [g] unless otherwise indicated).

[0147] Coloring was carried out on hair tresses about 5 cm long andweighing about 0.5 g. 1 g of the formulation to be tested was applied tothe hair. After 20 minutes (oxidation with air), the formulation wasrinsed out with water and the hair was washed with a commerciallyavailable shampoo. The colors listed in Table 2 correspond to theconditions after storage of the tresses for one day at room temperatureunder standard air humidity conditions (ca. 50% relative humidity).TABLE 1 formulations Component E1 E2 C1 C2 C3 ∃ Stenol7 1618 O¹ 6.7 6.76.7 6.7 6.7 ∃ Lorol7 techn² 2.0 2.0 2.0 2.0 2.0 ∃ Eumulgin7 B 2³ 2.0 2.02.0 2.0 2.0 ∃ Ascorbic acid 0.2 0.2 0.2 0.2 0.2 ∃ Ammonium sulfate — —1.0 — — ∃ 5,6-Dihydroxy- 1.0 — 1.0 1.0 — indoline hydrobromide ∃5,6-Diacetoxyindole — 1.0 — — 1.0 ∃ Potassium hydroxide — — X X X to pH9.5 ∃ Arginine (to pH 9.5) 3.0 3.0 — — — ∃ Water <−−−−−−−−−−−−−−to100−−−−−−−−−−−−−−−>

[0148] TABLE 2 colors [depth of color/shade] Formulation Grey human hairBlond human hair (Klugmann natural medium (Kerling natural white) grey#6623) E1 Medium blond dark blond/ Medium brown/ grey with slight bluetinge with slight blue tinge (flat medium brown) E2 Medium blond/ Lightbrown/ grey with slight blue tinge neutral, no blue tinge visible C1Medium blond/ Light brown/ natural color with slight natural color withslight red red tinge tinge C2 Light blond-medium blond/ Dark blond/bluish with slight blue tinge C3 Light blond/ Dark blond/ slight bluetinge neutral, no blue tinge visible

What is claimed is:
 1. A composition for coloring keratin fiberscomprising: a) a dye precursor comprising, an indoline, an indol, or aderivative thereof; and b) an amino acid or an oligopeptide
 2. Thecomposition of claim 1 wherein the amino acid or the oligopeptide formsa 2.5 percent by weight solution in water having a pH above
 9. 3. Thecomposition of claim 1 wherein the amino acid comprises analpha-aminocarboxylic acid.
 4. The composition of claim 3 wherein thealpha-aminocarboxylic acid is arginine, ornithine, lysine or histidine.5. The composition of claim 1 wherein the indoline or indole derivativecontains at least one hydroxy or amino group on the six-membered ring.6. The composition of claim 1 wherein the dye precursor is a derivativeof 5,6-dihydroxyindoline corresponding to formula (Ia): (Ia) wherein, R¹is hydrogen, a C₁₋₄ alkyl group or a C₁₋₄ hydroxyalkyl group, R² ishydrogen or a —COOH group or salt thereof, R³ is hydrogen or a C₁₋₄alkyl group, R⁴ is hydrogen, a C₁₋₄ alkyl group or a group —CO—R⁶ whereR⁶ is a C₁₋₄ alkyl group, R⁵ stands for one of the groups mentioned forR⁴, or a physiologically compatible salt of these compounds with anorganic or inorganic acid.
 7. The composition of claim 1 wherein dyeprecursor is a derivative of 5,6-dihydroxyindole corresponding toformula (Ib): (Ib) wherein, independently of one another, R¹ ishydrogen, a C₁₋₄ alkyl group or a C₁₋₄ hydroxyalkyl group, R² ishydrogen or a —COOH group or salt thereof, R³ is hydrogen or a C₁₋₄alkyl group, R⁴ is hydrogen, a C₁₋₄ alkyl group or a group —CO—R⁶ whereR⁶ is a C₁₋₄alkyl group, R⁵ stands for one of the groups mentioned forR⁴, or a physiologically compatible salt of these compounds with anorganic or inorganic acid.
 8. The composition of claim 1 wherein the dyeprecursor is a derivative of 5,6-dihydroxyindoline,N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline,N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline,5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole,N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole,N-butyl-5,6-dihydroxyindole 5,6-dihydroxyindolr-2-carboxylic acid, 4-,6- and 7-hydroxyindole, 6-amioindole, or 4-aminoindole andphysiologically compatible salts thereof.
 9. The composition of claim 1wherein said composition is free from oxidation dye precursors of theprimary intermediate type.
 10. The composition of claim 1 furthercomprising a primary intermediate selected from the group consisting ofp-phenylenediamine, p-toluylenediamine, p-aminophenol,1-(2′-hydroxyethyl)-2,5-diaminobenzene, 4-amino-3-methylphenol,4-amino-2-((diethylamino)-methyl)-phenol, 2,4,5,6-tetraaminopyrimidine,2-hydroxy-4,5,6-triamiopyrimidine and4-hydroxy-2,5,6-triaminopyrimidine.
 11. The composition of claim 1wherein said composition is free from oxidation dye precursors of thesecondary intermediate type.
 12. The composition of claim 1 furthercomprising a secondary intermediate selected from the group consisting1-naphthol, pyrogallol, 1,5-, 2,7-, and 1,7-dihydroxynaphthalene,3-aminophenol, 5-amino-2-methylphenol, 2-amino-3-hydroxypyridine,resorcinol, 4-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol,2-methyl resorcinol, 5-methyl resorcinol, 2,5-dimethyl resorcinol,2,6-dihydroxy-3,4-diaminopyridine, and physiologically compatible saltsthereof.
 13. The composition of claim 1 further comprising a substantivedye selected from the group consisting of HC Yellow 2, HC Yellow 4, HCYellow 5, HC Yellow 6, Basic Yellow 57, Disperse Orange 3, HC Red 3, HCRed BN, Basic Red 76, HC Blue 2, HC Blue 12, Disperse Blue 3, Basic Blue99, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9,Basic Brown 16, Basic Brown 17,4-amino-2-nitrodiphenylamine-2′-carboxylic acid,6-nitro-1,2,3,4-tetrahydroquinoxaline, hydroxyethyl-2-nitrotoluidine,picramic acid, 2-amino-6-chloro-4-nitrophenol,4-ethylamino-3-nitrobenzoic acid and2-chloro-6-ethylamino-1-hydroxy-4-nitrobenzene.
 14. The composition ofclaim 1 further comprising a naturally occurring substantive dyeselected from the group consisting of henna red, henna neutral, hennablack, camomile blossom, sandalwood, black tea, black alder bark, sage,logwood, madder root, catechu, sedre and alkanet.
 15. The composition ofclaim 14 comprising 0.1 to 20 percent by weight dye precursors andsubstantive dyes.
 16. The composition of claim 15 comprising 0.5 to 5percent by weight dye precursors and substantive dyes.
 17. Thecomposition of claim 1 comprising 0.05 to 10 percent by weight of theindole, indoline, or derivative thereof.
 18. The composition of claim 1comprising 0.2 to 5 percent by weight of the indole derivative orindoline derivative.
 19. The composition of claim 1 comprising 0.1 to 10percent by weight of the amino acid or the oligopeptide.
 20. A processfor intensifying or shading the coloring of keratin fibers comprising:(a) forming a coloring composition comprising an indoline, an indole, ora derivative thereof and an amino acid or oligopeptide; (b) applyingsaid coloring composition to keratin fibers.
 21. The process of claim 20wherein the keratin fibers comprise human hair.
 22. The process of claim20 wherein the coloring composition has a pH of 5to
 11. 23. The processof claim 22 wherein the coloring composition has a pH of 7 to
 10. 24.The process of claim 20 further comprising developing the final color ofthe keratin fibers using atmospheric oxygen as the sole oxidizing agent.25. The process of claim 20 further comprising repeating application ofthe coloring composition, followed after each application by oxidationwith atmospheric oxygen, for multiple times to effect the desired finalcolor.